Polymerizable diketopyrrolopyrroles and polymers prepared therewith

ABSTRACT

1,4-Diketopyrrolopyrroles of the formula in which A and B independently of one another are a group of the formula R1 is a long-chain radical containing a reactive group capable of polymerization, and R2 is C1-C6alkyl,  or R1. For the definition of the radicals R3-R9, refer to claim 1. The novel diketopyrrolopyrroles are suitable for preparing colored polymers with unexpectedly advantageous color effects.

This application is a divisional of 08/789,893 filed Jan. 29, 1997.

The present invention relates to novel diketopyrrolopyrroles containingpolymerizable reactive groups, and to polymers prepared therewith.

The diketopyrrolopyrrole pigments which are now referred to in theliterature as well, for example in the Colour Index, as DPP pigments,and which have been known for some years and found to be useful, aredescribed inter alia in U.S. Pat. No. 4,415,685 and U.S. Pat. No.4,579,949.

EP-A 337 951 describes coloured polymer microparticles which can beobtained by copolymerizing pigment derivatives which containpolymerizable reactive groups into various kinds of polymers. Mention ismade in this context of derivatives of a wide variety of classes ofpigment, including DPP derivatives, and specifically one member thereof,a 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole substituted on bothnitrogen atoms by an ethyl methacrylate group.

However, it has been found that the copolymerization of this compounddoes not take place satisfactorily.

It has now been found that it is nevertheless possible, by introducingspecific, long-chain reactive groups, to obtain DPP chromophores which,surprisingly, can be reacted readily with polymers or to form polymers,whether directly, by homo- or copolymerization, or else by grafting ontoexisting, preformed homo- or copolymers.

The present invention accordingly provides 1,4-diketopyrrolopyrroles ofthe formula ##STR4## in which A and B independently of one another are agroup of the formula ##STR5## in which R₃ and R₄ independently of oneanother are hydrogen, halogen, C₁ -C₁₈ alkyl,

C₁ -C₁₈ alkoxy, C₁ -C₁₈ alkylmercapto, C₁ -C₁₈ alkylamino, C₁ -C₁₈alkoxycarbonyl,

C₁ -C₁₈ alkylaminocarbonyl, --CN, --NO₂, trifluoromethyl, C₅ -C₆cycloalkyl,

--C═N--(C₁ -C₁₈ alkyl), ##STR6## imidazolyl, pyrazolyl, triazolyl,piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl,benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl,

G is --CH₂ --, --CH(CH₃)--, --C(CH₃)₂ --, --CH═N--, --N═N--, --O--,--S--, --SO--, --SO₂ --, --CONH-- or --NR₉ --,

R₅ and R₆ independently of one another are hydrogen, halogen, C₁ -C₆alkyl,

C₁ -C₁₈ alkoxy or --CN,

R₇ and R₈ independently of one another are hydrogen, halogen or C₁ -C₆alkyl and

R₉ is hydrogen or C₁ -C₆ alkyl,

R₁ is a radical having at least 4 carbon atoms and containing apolymerizable reactive group, and

R₂ is C₁ -C₆ alkyl, ##STR7## or R₁.

The term polymerizable reactive groups refers, for example, to groupscapable of addition polymerization, for example acrylate radicals, orgroups capable of condensation polymerization, for example hydroxyl oracid chloride groups, or else groups capable of polyaddition, forexample hydroxyl or isocyanate groups.

Preferably

R₁ is a radical of the formula

    --(CH.sub.2).sub.m --CH═CH--(CH.sub.2).sub.n --CH.sub.3(II)

or

    --(Y).sub.p --X--(Z).sub.r --Q                             (III)

in which m and n independently of one another are an integer betweenzero and 12, with the proviso that the sum m+n is at least 4, and p andr independently of one another are zero or 1,

X is uninterrupted C₄ -C₁₈ alkylene or is C₄ -C₁₈ alkylene which isinterrupted one or more times by --O-- and/or --S--, --NH--, phenylene,--COO--, --CONH-- or ##STR8## in which R₁₀ is hydrogen or methyl, Y is##STR9## --Si(Cl)₂ --, --Si(OC₂ H₅)₂ --, --Si(OCOCH₃)₂ --, --CH₂-CH(OH)-- or --CH(CN)--

and

Z is --O--, --NH--, --COO--, phenylene, ##STR10## --Si(Cl)₂ --, --Si(OC₂H₅)₂ -- or --Si(OCOCH₃)₂ --,

Q is --OH, --NH₂, glycidyl, ##STR11## --CHO, --NCO, --CH═CH₂,--C(CH₃)═CH₂, --CO--CH═CH₂, --CO--C(CH₃)═CH₂, C₅ -C₇ cycloalkenyl,##STR12## --CONHR₁₁, --COOR₁₁ or --COR₁₁, in which R₁₁ is hydrogen or C₁-C₆ alkyl,

or Q is ##STR13## in which s is an integer from 1 to 6 such as 1, 2, 3,4, 5 or 6.

Any halogen substituents are generally iodine, fluorine, bromine orchlorine, preferably bromine or chlorine, particularly preferablychlorine;

the C₁ -C₄ alkyl radical is methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl or tert-butyl;

C₁ -C₆ alkyl is, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl or hexyl;

the C₁ -C₁₈ alkyl radical is, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl,hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl,hexadecyl or octadecyl;

C₄ -C₁₈ alkylene, preferably the linear representatives, can for examplebe --(CH₂)₄ --, --(CH₂)₅ --,

--(CH₂)₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --(CH₂)₉ --, --(CH₂)₁₀ --,--(CH₂)₁₁ --, --(CH₂)₁₂ --, --(CH₂)₁₃ --, --(CH₂)₁₄ --,

--(CH₂)₁₅ --, --(CH₂)₁₆ --, --(CH₂)₁₇ --, --(CH₂)₁₈ --, preferably C₄-C₁₂ alkylene such as --(CH₂)₄ --, --(CH₂)₅ --,

--(CH₂)₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --(CH₂)₉ --, --(CH₂)₁₀ --,--(CH₂)₁₁ --, or --(CH₂)₁₂ --;

C₁ -C₁₈ alkoxy is, both alone and in C₁ -C₁₈ alkoxycarbonyl, for examplemethoxy, ethoxy, n-propoxy, isopropoxy, butyloxy, hexyloxy, decyloxy,dodecyloxy, hexadecyloxy or octadecyloxy, preferably C₁ -C₆ alkoxy suchas methoxy, ethoxy, n-propoxy, isopropoxy, butyloxy, hexyloxy;

C₁ -C₁₈ alkylmercapto is, for example, methylmercapto, ethylmercapto,propylmercapto, butylmercapto, octylmercapto, decylmercapto,hexadecylmercapto or octadecylmercapto;

C₁ -C₁₈ alkylamino is, both alone and in C₁ -C₁₈ alkylaminocarbonyl, forexample methylamino, ethylamino, propylamino, hexylamino, decylamino,hexadecylamino or octadecylamino, preferably C₁ -C₆ alkylamino such asmethylamino, ethylamino, propylamino or hexylamino.

C₅ -C₆ cycloalkyl is, for example, cyclopentyl or cyclohexyl, especiallycyclohexyl.

C₅ -C₇ cycloalkenyl is mono- or bicyclic cycloalkenyl, for examplecyclopentenyl, cyclohexenyl or norbornenyl.

Some examples of R₁ as a radical of the formula III are

--(CH₂)₆ --OH, --(CH₂)₁₀ --OH, --(CH₂)₁₁ --OH, --(CH₂)₆ --OCO--CH═CH₂,--(CH₂)₆ --OCO--C(CH₃)═CH₂,

--(CH₂)₁₀ --OCO--CH═CH₂, --(CH₂)₁₀ --OCO--C(CH₃)═CH₂, --(CH₂)₁₁--OCO--CH═CH₂, --(CH₂)₁₁ --OCO--C(CH₃)═CH₂,

--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --OH

--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --O--CO--CH═CH₂

--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --O--CO--C(CH₃)═CH₂ ##STR14## --(CH₂)₃--S--(CH₂)₂ --OH --(CH₂)₃ --S--(CH₂)6--OH

--(CH₂)₃ --S--(CH₂)₂ --COOH

--(CH₂)₃ --S--(CH₂)₆ --COOH

--(CH₂)₃ --S--(CH₂)₂ --NH₂ ##STR15## --(CH₂)₆ --O--Si(Cl₂)--CH═CH₂--(CH₂)₆ --O--Si(OC₂ H₅)₂ --CH═CH₂

--(CH₂)₆ --O--Si(O--COCH₃)₂ --CH═CH₂

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂)₂ --OH

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂)₆ --OH

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂)₂ --COOH

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂)₂ --NH₂

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂)₆ --NH₂

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH

--Si(Cl)₂ --(CH₂)₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ NH₂

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂)₂ --OH

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂)₆ --OH

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂)₂ --COOH

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂)₆ --COOH

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂)₂ --NH₂

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂ O₆ --NH₂

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH

--Si(OC₂ H₅)₂ --(CH₂)₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ NH₂

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂ O₂ --OH

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂)₆ --OH

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂)₂ --COOH

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂)₆ --COOH

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH)₂ --NH₂

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂)₆ --NH₂

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH

--Si(OCOCH₃)₂ --(CH₂)₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ NH₂

--CH₂ CH(OH)--CH₂ --S--(CH₂)₆ --COOH

--CH₂ CH(OH)--CH₂ --S--(CH₂)₆ --OH

--CH₂ CH(OH)--CH₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH

--CH₂ CH(OH)--CH₂ --S--(CH₂ CH₂ O)₂ --CH₂ CH₂ COOH

--CH₂ CH(OH)--CH₂ --NH--(CH₂)₆ --COOH

--CH₂ CH(OH)--CH₂ --NH--(CH₂)₆ --OH

--CH₂ CH(OH)--CH₂ --NH--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH

--CH₂ --CONH--(CH₂)₆ --OH

--CH₂ --CONH--(CH₂)₆ --COOH

--CH₂ --CONH--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH ##STR16## --CH(CN)--(CH₂)₆ --OHCH(CN)--(CH₂ CH₂ O)₂ --CH₂ CH₂ OH

--(CH₂)₆ --O--CH₂ CH₂ O--CH═CH₂

--(CH₂)₆ O--CH₂ --CH═CH₂

--(CH₂)₆ --O--CH═CH₂

--(CH₂)₆ --O--CH₂ --CO--CH═CH₂

--(CH₂)₆ --O--CO--CH═CH₂

--(CH₂)₆ --O--(CH₂)₂ --NHCO--CH═CH₂

--(CH₂)₆ --O--CH₂ --COO--CH═CH₂ ##STR17## --(CH₂)₆ --O--CH₂ --CHO--(CH₂)₆ --O--CH₂ --NCO ##STR18## --(CH₂)₃ --S--(CH₂)₂ --CO--O--CO--CH₃.

Of particular interest are the novel diketopyrrolopyrroles of theformula I in which A and B independently of one another are a group ofthe formula ##STR19## in which R₃ and R₄ independently of one anotherare hydrogen, halogen such as chlorine or bromine, C₁ -C₄ alkyl, C₁ -C₆alkoxy, C₁ -C₆ alkylamino or CN,

G is --O--, --NR₉ --, --N═N-- or --SO₂ --,

R₅ and R₆ are hydrogen, and

R₉ is hydrogen, methyl or ethyl,

and especially those in which, in the formula I, A and B are identicaland are a group of the formula ##STR20## in which R₃ and R₄independently of one another are hydrogen, methyl, tert-butyl, chlorine,bromine or CN. R₄ is preferably hydrogen. Of particular significance arethose novel diketopyrrolopyrroles of the formula I in which R₁ is aradical of the formula

    --X--(O).sub.r --Q                                         (IV)

in which

X is uninterrupted C₄ -C₁₂ alkylene or is C₄ -C₁₂ alkylene which isinterrupted 1, 2 or 3 times by O and/or once by --S--, --NH-- or##STR21## r and R₁₀ are as defined above, and Q is --OH ; --CH═CH₂,--C(CH₃)═CH₂, --CO--CH═CH₂ or --CO--C(CH₃)═CH₂.

X is preferably --(CH₂)_(q) --, where q can be an integer between 6 and12, such as 6, 7, 8, 9, 10, 11 or 12,

--(CH₂ CH₂ O)₂ --CH₂ CH₂ --, or ##STR22## R₂ is preferably CH₃ or R₁,subject to the same preferences as for R₁.

The novel diketopyrrolopyrroles of the formula I in which R₁ is aradical of the formula II or III and R₂ is C₁ -C₆ alkyl or ##STR23##which are preferably prepared by reacting a pyrrolinone of the formula##STR24## in which R is preferably C₁ -C₄ alkyl, with a nitrile of theformula

    B--CN                                                      (VI)

where A and B are as defined above, to give the diketopyrrolopyrrole ofthe formula ##STR25## which is reacted further with a compound of theformula

    R.sub.1 --Hal                                              (VII)

or, if Y in the radical with the formula III is --CH₂ --CH(OH)--, with acompound of the formula ##STR26## in which R₁, X, Z, Q and r are asdefined above and Hal is preferably chlorine or bromine.

The reaction parameters can be chosen, for example, in analogy to themethod described in U.S. Pat. No. 4,778,899 and consequently furtherdetails on this subject are unnecessary.

Novel diketo pyrroles of the formula I in which R₁ and R₂ are identicalare obtained analogously, in a preferred embodiment, starting from adiketopyrrolopyrrole of the formula ##STR27## (obtainable, for example,by the method described in U.S. Pat. No. 4,579,949) using correspondingamounts of the compounds of the formulae VII and VIII.

Diketopyrrolopyrroles of formula I in which Q for example is--CO--CH═CH₂ or --CO--C(CH₃)═CH₂ and r is 1 can be prepared, in afurther preferred embodiment, by reacting diketopyrrolopyrroles of theformula I in which Q is --OH with acryloyl chloride or methacryloylchloride, respectively. In a similar manner it is also possible, forexample, to introduce the groups --Si(Cl)₂ --CH═CH₂, --Si(OC₂ H₅)₂--CH═CH₂, --Si(OCOCH₃)₂ --CH═CH₂, --CONHR₁₁, --COOR₁₁ etc., as Q or Z--Qrespectively.

Pyrrolinones of the formula V are conventionally obtained by methodsknown per se, for example by cyclizing a compound of the formula##STR28## in which A and R are as defined above, with an ammonium salt,to give the pyrrolinone of the formula ##STR29## as described, forexample, in U.S. Pat. No. 4,778,899, and reacting it further with acompound of the formula R₂ -Hal, in which R₂ is C₁ -C₆ alkyl or##STR30## in accordance with generally known methods.

The compounds of the formulae VI, VII, VIII, IX and X are known and/orcan be prepared in analogy to generally known techniques.

The novel DPP compounds can be used very readily, by virtue of theirreactive groups, for preparing or modifying polymers by a polymerizationreaction or a polymer-analogous reaction. The coloured polymers modifiedor prepared in this way unexpectedly exhibit advantageous colour effectsand--depending on the amount of DPP compound used--a wide variety ofshades, which may differ entirely from those of the corresponding DPPpigments which possess no groups capable of polymerization.

The present invention provides, furthermore, a process for preparing ormodifying polymers by polymerization or polymer-analogous reaction,which involves polymerizing a diketopyrrolopyrrole of the formula I, inthe presence if desired of an appropriate, preferably customarycomonomer, for example one carrying at least one carbon-carbon doublebond, or of a polymer which carries polymerizable groups.

In a preferred embodiment of this invention coloured (co)polymers can beprepared by polyreacting a mixture of the novel DPP momoners and furthercustomary and suitable monomers in a liquid phase, e.g. in a melt,solution, suspension or emulsion.

These novel DPP polymers are commonly prepared in accordance withgenerally known methods, for example either by a polymerizationreaction, i.e. by addition polymerization (thermal or photochemical),condensation polymerization or polyaddition, or by a polymer-analogousreaction, i.e. by reacting the novel DPP compounds, containing suitablereactive groups, with existing polymers which themselves have reactivegroups (grafting).

In accordance with observations made to date, the novel DPP compounds(DPP monomers) can be used to conduct all known types of polymerizationreaction. Thus it is possible, for example, to use DPP monomers whosereactive groups have C═C bonds to prepare vinyl, allyl, vinyl ester,vinyl amide, vinyl acetate or vinyl ketone polymers; to usemonofunctional DPP monomers whose reactive groups contain heteroatoms toprepare polyaldehydes, polyisocyanates, polyepoxides, polyethers,polyacetones or polylactams; to use bifunctional DPP monomers whosereactive groups contain heteroatoms to prepare polyesters, polyamides,polyimides or polycarbonates by way of condensation polymerization, andpolyepoxides, polyurethanes or polyimides by way of polyaddition, itbeing possible for the polymerization to involve free-radical, cationicor anionic polymerization, coordination polymerization or group-transferpolymerization.

Examples of the preparation of DPP polymers, starting from the novel DPPmonomers, include:

Addition polymerization: DPP polyacrylates by free-radical thermalpolymerization of DPP acrylates; DPP polyacrylates by free-radicalphotopolymerization of DPP acrylates.

Condensation polymerization: DPP polyesters from DPP diols and di-acidchlorides; DPP polycarbonates from DPP diols and phosgene.

Polyaddition: DPP polyurethanes from DPP diols and diisocyanates; DPPpolyepoxides from DPP epoxides and amines.

Polymer-analogous reaction: Reaction of a DPP alcohol with a polymerwhich has been prepared from styrene and maleic anhydride, and thuscontains anhydride groups, to form a polymer containing DPP mono- ordiester groups.

The novel DPP polymers may also include additives, such as lightstabilizers, antioxidants and UV absorbers, which can be added during orafter actual polymerization, also for example during the processing ofthe polymers (extrusion). These additives may themselves also havepolymerizable reactive groups, and in this case can be copolymerizedtogether with the DPP monomers.

The DPP polymers prepared in accordance with this invention and whichhereinafter will be understood as including also copolymers preparedfrom novel DPP polymers and other customary monomers, are advantageouslysuited to many purposes, such as for colouring high molecular weightorganic materials, e.g. biopolymers, plastic materials, includingfibres, glasses, ceramic products, for formulations in decorativecosmetics, for the preparation of inks, printing inks, paint systems, inparticular automotive lacquers and photoresists, photo-andelectroconductive polymers, fluorescent whitening agents, photocellaggregates, coloured photoresists and dispersion colours and,furthermore, the novel diketopyrrolopyrroles can be used in thebiomedical field of application, e.g. for the preparation of diagnosticagents as well as in the fields of impact-printing andnon-impact-printing and photo/repro in general.

Illustrative examples of suitable organic materials of high molecularweight which can be coloured with the DPP polymers of this invention arevinyl polymers, for example poly-styrene, poly-α-methylstyrene,poly-p-methylstyrene, poly-p-hydroxystyrene,poly-p-hydroxy-phenylstyrene, polymethyl methacrylate and polyacrylamideas well as the corresponding methacrylic compounds, polymethylmaleate,polyacrylonitrile, polymethacrylonitrile, polyvinyl chloride, polyvinylfluoride, polyvinylidene chloride, polyvinylidene fluoride, polyvinylacetate, polymethyl vinyl ether and polybutyl vinyl ether; polymerswhich are derived from maleinimide and/or maleic anhydride, such ascopolymers of maleic anhydride with styrene; polyvinyl pyrrolidone; ABS;ASA; polyamides; polyimides; polyamidimides; polysulfones; polyethersulfones; polyphenylene oxides; polyurethanes; polyureas;polycarbonates; polyarylenes; polyarylene sulfides; polyepoxides;polyolefins such as polyethylene and polypropylene; polyalkadienes;biopolymers and the derivatives thereof e.g. cellulose, cellulose ethersand esters such as ethylcellulose, nitrocellulose, cellulose acetate andcellulose butyrate, starch, chitin, chitosan, gelatine, zein; naturalresins; synthetic resins such as alkyd resins, acrylic resins, phenolicresins, epoxide resins, aminoformaldehyde resins such asurea/formaldehyde resins and melamine/formaldehyde resin; vulcanizedrubber; casein; silicone and silicone resins; rubber, chlorinatedrubber; and also polymers which are used, for example, as binders inpaint systems, such as novolaks which are derived from C₁ -C₆ -aldehydessuch as formaldehyde and acetaldehyde and a binucluear or mononuclear,preferably mononuclear, phenol which, if desired, is substituted by oneor two C₁ -C₉ alkyl groups, one or two halogen atoms or one phenyl ring,such as o-, m- or p-cresol, xylene, p-tert-butylphenol, o-, m- orp-nonylphenol, p-chlorophenol or p-phenylphenol, or a compound havingmore than one phenolic group such as resorcinol,bis(4-hydroxyphenyl)-methane or 2,2-bis(4-hydroxyphenyl)propane; as wellas suitable mixtures of said materials.

Particularly preferred high molecular weight organic materials, inparticular for the preparation of a paint system, a printing ink or ink,are, for example, cellulose ethers and esters, e.g. ethylcellulose,nitrocellulose, cellulose acetate and cellulose butyrate, natural resinsor synthetic resins (polymerization or condensation resins) such asaminoplasts, in particular urea/formaldehyde and melamine/formaldehyderesins, alkyd resins, phenolic plastics, poly-carbonates, polyolefins,polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyester,ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone andsilicone resins as well as their possible mixtures with one another.

It is also possible to use high molecular weight organic materials indissolved form as film formers, for example boiled linseed oil,nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde andurea/formaldehyde resins as well as acrylic resins.

Said high molecular weight organic compounds may be obtained singly orin admixture, for example in the form of granules, plastic materials,melts or in the form of solutions, in particular for the preparation ofspinning solutions, paint systems, coating materials, inks or printinginks.

In a particularly preferred embodiment of this invention, the novel DPPpolymers are used for the mass coloration of polyvinyl chloride,polyamides and, especially, polyolefins such as polyethylene andpolypropylene as well as for the preparation of paint systems, includingpowder coatings, inks, printing inks and coating colours.

Illustrative examples of preferred binders for paint systems arealkyd/melamine resin paints, acryl/melamine resin paints, celluloseacetate/cellulose butyrate paints and two-pack system lacquers based onacrylic resins which are crosslinkable with polyisocyanate. According toobservations made to date, the novel DPP polymers can be added in anydesired amount to the material to be coloured, depending on the end userequirements. In the case of high molecular weight organic materials,for example, the pigments composed according to this invention can beused in an amount in the range from 0.01 to 40, preferably from 0.1 to20% by weight, based on the total weight of the coloured high molecularweight organic material.

The pigmenting of the high molecular weight organic materials with thenovel DPP polymers is usually effected by incorporating said novel DPPpolymers, if desired in the form of masterbatches, in the high molecularweight organic materials using customary apparatus suitable to this end,such as extruders, roll mills, mixing or milling apparatus. The materialthus treated is then normally brought into the desired final form bymethods which are known per se, such as calendering, moulding, extrusionmoulding, coating, casting, extruding, or by injection moulding.

In a preferred embodiment of this invention, the novel DPP monomers canbe polyreacted in an extruder together with other monomers, inparticular with those monomers which are customarily used for thepreparation of the aforementioned polymers (reactive extrusion, forexample in general accordance with the process disclosed in EP-A 337951). Copolymers prepared in this manner usually have the same spectrumof application as the blends so far cited consisting of novel DPPpolymers and high molecular weight organic materials.

To produce non-brittle mouldings or to diminish their brittleness,so-called plasticizers can be added to the high molecular weightsubstances prior to moulding. Plasticizers may be, for example, estersof phosphoric acid, phthalic acid and sebacic acid. Said plasticizersmay be added before, during or after pigmenting the high molecularweight substances with the DPP polymers of this invention.

To obtain different shades, the novel DPP polymers may advantageously beused in admixture with fillers, transparent and opaque white, colouredand/or black pigments as well as customary luster pigments in thedesired amount.

For the preparation of paints systems, coating materials, inks andprinting inks, the corresponding high molecular weight organicsubstances, such as binders, synthetic resin dispersions etc. and thenovel DPP polymers are usually dispersed or dissolved together, ifdesired together with customary additives such as fillers, paintauxiliaries, siccatives, plasticizers and/or additional pigments, in acommon solvent or mixture of solvents. This can be achieved bydispersing or dissolving the individual components by themselves, oralso several components together, and only then bringing all componentstogether, or by adding everything together at once.

For application in printing, all customary industrial printing processescan be employed, such as screen printing, rotogravure, bronze printing,flexographic printing and offset printing.

The Examples which follow illustrate the invention.

Preparation of DPP monomers

EXAMPLE 1

a) 29.8 g (0.12 mol) of the pyrrolinone of the formula ##STR31##prepared in accordance with the method described in Example 4 of U.S.Pat. No. 4,778,899, and 18.16 g (0.132 mol) of p-chlorobenzonitrile areplaced in a sulfonating flask, with nitrogen flushing, and 180 ml of2-methyl-1-pentanol are added. The mixture is heated at 110-115° C.until, after about 30 minutes, a clear, light brown solution is formed.Subsequently, 12.96 g (0.24 mol) of 30% sodium methylate in saturatedsodium hydroxide solution are metered in over the course of 2 hours at astirring speed of 510-520 rpm, with simultaneous removal, bydistillation, of the methanol/ethanol mixture which is formed. Stirringis continued at the same temperature for about one hour, and the mixtureis then cooled to room temperature. Following the addition of 500 ml ofmethanol, the mixture is acidified with 57.7 g (0.96 mol) of aceticacid. Vigorous stirring of the thick slurry which forms produces, afterabout 3 minutes, an intensely orange-red coloured precipitate. Thisproduct is diluted with a further 100 ml of methanol and with 150 ml ofwater, and the orange-red suspension is filtered. The filter cake iswashed with 150 ml of methanol in 3 portions and dried overnight at60-70° C. in a vacuum oven, to give 25.53 g (63.2% of theory) of thediketopyrrolopyrrole of the formula

    ______________________________________                                        (XII)                                                                             #STR32##                                                                  Analysis:  C       H          N     Cl                                        ______________________________________                                        calculated:                                                                              67.76%  3.89%      8.32% 10.53%                                      found: 67.62% 3.93% 8.26% 10.47%                                            ______________________________________                                    

b) 10.10 g (0.030 mol) of the diketopyrrolopyrrole of the formula XII(Example 1a), 2.50 g (0.018 mol) of potassium carbonate and 100 ml ofdimethylacetamide are placed in a sulfonating flask, with nitrogenflushing, and the mixture is heated with stirring at 130-135° C. After30 minutes at this temperature, a strongly dark red-brown suspension isobtained to which 7.23 g (0.0375 mol) of 10-chloro-1-decanol, dilutedwith 10 ml of dimethylacetamide, are added dropwise over the course of 1hour. After this mixture has been stirred at the same temperature for 4hours, a further 2.90 g (0.015 mol) of 10-chloro-1-decanol, diluted with10 ml of dimethylacetamide, are added dropwise over the course of 15minutes, and stirring is continued, under continual nitrogen flushing,for 4 hours more before the mixture is cooled to room temperature. Thedark red-brown solution is subsequently filtered off cold, the filterresidue is washed three times with 5 ml of dimethylacetamide, and thefiltrate is concentrated to dryness in a rotary evaporator. The crudeproduct is purified by means of column chromatography over silica gel 60using 9:1 toluene/dioxane as eluent, to give 6.25 g (42.3%) of thecompound of the formula ##STR33## as a dark red oil.

The NMR spectrum in CDCl₃ /p.a. agrees completely with the targetstructure.

EXAMPLE 2

In a sulfonating flask thoroughly flushed with nitrogen, 26.94 g (0.08mol) of the diketopyrrolopyrrole of the formula XII (Example 1a) and26.85 g (0.195 mol) of potassium carbonate (both substances dried at350° C. beforehand) are weighed out, and 350 ml of dimethylformamide areadded. The mixture is heated with stirring to 120-125° C., and then50.50 g (0.195 mol) of 97% 11-bromo-1-undecanol, and dissolved in 100 mlof dimethylformamide, are added dropwise at this temperature over thecourse of 15 minutes. After the end of addition, a dark red-brownsuspension is left which is stirred further at 120-125° C. for 2 hoursand is then cooled to room temperature, during which the colour changesto yellow-brown. This suspension is stirred further at room temperatureovernight before being filtered, and the filter residue is washed with30 ml of dimethylformamide. The filtrate is concentrated to dryness in arotary evaporator. The crude product is purified by means of columnchromatography over silica gel 60 using 8:2 toluene/dioxane as eluent,to give 9.4 g (23.2% of theory) of the compound of the formula ##STR34##

The NMR spectrum in CDCl₃ /p.a. agrees with the target structure.

EXAMPLE 3

Under nitrogen, 6.73 g (0.012 mol) of the diketopyrrolopyrrole of theformula XIV (Example 2), 0.012 g (0.06 mmol) of phenothiazine and 110 mlof dichloroethane are placed in a sulfonating flask. The yellow-redsolution produced is heated to reflux temperature, and then 2.17 g(0.024 mol) of acryloyl chloride dissolved in 10 ml of dichloroethaneare added dropwise over the course of 15 minutes. After the end of theaddition, the mixture is stirred further at reflux (80° C.) for 7 hoursand then cooled to room temperature. The orange-red solution isextracted in a separating funnel by shaking 5 times with 30 ml of 5%sodium hydroxide solution and then 2 times with deionized water. Theorganic phase is dried over MgSO₄.H₂ O and filtered. After completeconcentration of the orange-red filtrate in a rotary evaporator, thecrude product is recrystallized from 60 ml of methanol, to give 6.1 g(81.9% of theory) of an orange-coloured product of the formula

    ______________________________________                                        (XV)                                                                              #STR35##                                                                  Analysis:  C       H          N     Cl                                        ______________________________________                                        calculated:                                                                              70.64%  6.5%       4.99% 6.32%                                       found: 70.30% 6.81% 5.10% 6.38%                                             ______________________________________                                    

EXAMPLE 4

a) Under nitrogen, 29.43 g (0.12 mol) of the pyrrolinone of formula XI(Example 1a) and 21.02 g (0.132 mol) of 4-tert-butylbenzonitrile areplaced in a sulfonating flask, and 180 ml of 2-methyl-1-pentanol areadded. The mixture is then heated with stirring to 115-120° C. until,after about 30 minutes, a clear, light brown solution is produced.Subsequently, 43.22 g (0.24 mol) of 30% sodium methylate in saturatedsodium hydroxide solution are metered in over the course of 2 hours at astirring speed of 510-520 rpm, with subsequent removal, by distillation,of the methanol/ethanol mixture which forms. After the end of additionof the sodium methylate, a dark violet solution is produced which issubsequently stirred at 115-120° C. for 30 minutes and then cooled toroom temperature. Following the addition of 600 ml of methanol, themixture is acidified with 57.7 g of acetic acid and diluted with 600 mlof water. Within the green-yellow solution, a dark oil is formed fromwhich an orange pigment crystallizes out by overnight stirring. Thispigment is filtered off, washed several times with methanol, and driedat 40-50° C. in a vacuum oven, to give 3.84 g of a red-orangecrystalline product of the formula ##STR36##

b) The procedure of Example 1b is repeated but replacing thediketopyrrolopyrrole of the formula XII by the equivalent amount of thediketopyrrolopyrrole of the formula XVI, to give the compound of theformula ##STR37##

EXAMPLE 5

The procedure of Example 1b is repeated but replacing the10-chloro-1-decanol by the by the equivalent amount of6-chloro-1-hexanol, to give the compound of the formula ##STR38##

EXAMPLE 6

20.21 g (0.060 mol) of the diketopyrrolopyrrole of the formula XII(Example 1a) are weighed out directly into a sulfonating flask which isflushed thoroughly with nitrogen, and then 270 ml of dimethylformamideare added, and the mixture is heated at 130-135° C. with stirring andwith nitrogen being supplied. After 30 minutes, 12.44 g (0.090 mol) ofpotassium carbonate (dried at 250° C.) are added. 15.18 g (0.090 mol) oftriethylene glycol monohydrin dissolved in 30 ml of dimethylformamideare added dropwise over the course of 15 minutes to the dark violetsuspension. The resulting dark brown suspension is stirred at 130-135°C. for 41/2 hours, then cooled to room temperature and stirred furtherovernight. It is subsequently filtered, and the filter residue is washedwith dimethylformamide. The filtrate is concentrated in a rotaryevaporator to a volume of about 150 ml. The product crystallizes out,and is recrystallized from 200 ml of ethanol and dried at 40-50° C. in avacuum oven, to give 8.42 g (30% of theory) of a crystalline product ofthe formula ##STR39## with a melting point of 163° C.

EXAMPLES 7-9

If, in a manner similar to that described in Example 3, adiketopyrrolopyrrole of the formula ##STR40## is reacted with an acidchloride of the formula ##STR41## then a product of the formula##STR42## is obtained in which X and Q are as defined in the tablebelow:

    ______________________________________                                        Example X                   Q                                                 ______________________________________                                        7       --(CH.sub.2).sub.6- --C(CH.sub.3) = CH.sub.2  .sup.                     8 --(CH.sub.2).sub.10- --CH = CH.sub.2                                        9 --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2- --CH                                  = CH.sub.2                                        ______________________________________                                    

EXAMPLE 10

2.35 g (0.005 mol) of the diketopyrrolopyrrole of the formula XIX(Example 6) and 30 ml of dichlorobenzene are placed under nitrogen in asulfonating flask, 5.0 mg (0.05 mmol) of thiodiphenylamine are added,and the mixture is heated with stirring at 110-115° C. 3.17 g (0.010mol) of the methyl-hexahydrophthalic acid derivative (isomer mixture) ofthe formula ##STR43## (obtained by generally known methods frommethylhexahydrophthalic anhydride and hydroxyethyl methacrylate) areadded dropwise with vigorous stirring over the course of 15 minutes tothe clear orange-red solution, stirring is continued for about 2 hoursat 110-115° C., and then the mixture is cooled to room temperature. Theclear dark red solution is washed in a separating funnel 3 times with 20ml of 5% sodium hydroxide solution and 2 times with 30 ml of deionizedwater, and the organic phase is dried over MgSO₄.H₂ O, filtered andconcentrated to dryness under a high vacuum. The resulting product isrecrystallized from 30 ml of ethanol, to give 3.05 g (81.3% of theory)of a crystalline product formula ##STR44## R= ##STR45## with a meltingpoint of 69.6° C.

EXAMPLE 11

34.60 g (0.12 mol) of diketopyrrolopyrrole of the formula ##STR46##(obtained by the method described in U.S. Pat. No. 4,579,949 (Ex. 26)),49.76 g (0.36 mol) of potassium carbonate (dried at 350° C.) and 600 mlof freshly distilled dimethylformamide are placed under nitrogen in asulfonating flask and are heated to 130-135° C. Then 51.80 g (0.36 mol)of 95% 6-chloro-1-hexanol are added dropwise at this temperature withvigorous stirring over the course of about 10 minutes. After the end ofthe addition, the dark red suspension is stirred further at 130-135° C.for 2 hours more and then at room temperature overnight. The resultingdark red solution containing suspended material (KCl, K₂ CO₃) isfiltered and the filter cake is washed three times with 25 ml ofdimethylformamide. The filtrate is added with further stirring to 2 l ofdistilled water, and an orange-coloured product precipitates. Themixture is heated at boiling and filtered at 94° C. The tacky red masswhich remains in the filter is dissolved hot in 800 ml of ethanol, andthe solution is concentrated to about 300 ml and left to standovernight, during which an orange-coloured product is precipitatedwhich, after cooling in ice-water, is filtered off and recrystallizedfrom ethanol, to give 15.1 g (26.5% of theory) of an orange crystallineproduct of the formula

    ______________________________________                                          #STR47##                                                                    Analysis: C            H       N                                              ______________________________________                                        calculated:                                                                             73.74%       7.43%   5.73%                                            found: 73.51% 7.47% 5.66%                                                   ______________________________________                                    

EXAMPLE 12

19.55 g (0.04 mol) of the product from Example 11, 0.04 g (2·10⁻⁴ mol)of phenothiazine and 380 ml of dichloroethane are placed under nitrogenin a sulfonating flask, and the mixture is heated to reflux. The cloudy,orange-coloured solution is treated by dropwise addition, over thecourse of about 30 minutes under reflux (80° C.) and with stirring, of14.48 g (0.16 mol) of acryloyl chloride. After the end of the addition,washing is carried out with 20 ml of dichloroethane. The yellow-orangesolution is stirred at reflux for 7 hours and then cooled to roomtemperature and left to stand overnight. The orange-red, very slightlycloudy solution is washed in a separating funnel 5 times with 100 ml of5% sodium hydroxide solution and 2 times with deionized water, driedover MgSO₄.H₂ O and filtered. The clear, orange-red filtrate isevaporated completely in a rotary evaporator. The red oil which remainssolidifies overnight to form a solid mass which is recrystallized fromethanol, to give 23.1 g (96.7% of theory) of a crystalline product ofthe formula ##STR48## with a melting point of 79.7-80.1 ° C. Preparationof DPP polymers

EXAMPLE 13

5.13 g (0.01 mol) of the product from Example 11 and 60 ml ofchlorobenzene are placed under nitrogen in a sulfonating flask andheated to reflux. At 120° C. a further 30 ml of chlorobenzene are added.1.68 g (0.01 mol) of hexamethylene duisocyanate are added dropwise overthe course of 15 minutes, with stirring and at 130° C. to the slightlycloudy solution. About 40 minutes after the end of the addition, withthe temperature unchanged, a clear solution is present. After a reactiontime of 75 minutes, 0.0 13 g of dimethylcyclohexylamine (1.0 mol %solution in chlorobenzene) is added as catalyst. After a further 31/2hours, the solution changes into a fine suspension. This suspension isstirred overnight at 129° C. and then cooled to room temperature. Theorange-red suspension is filtered and the product is dried in vacuo at60-70° C., to give 6.3 g (92.5% of theory) of the desired polyurethanewith a sharply defined melting point of 142.8° C. The IR (KBr disc)clearly shows the characteristic urethane band at 2330 cm⁻¹.

EXAMPLE 14 Photocuring of a DPP Bisacrylate Monomer

0.8 g of the product from Example 12 is mixed at 60° C. with 7.2 g ofCibatool®SL 5154 (a blend comprising acrylate monomers, photoinitiatorand sensitizer, CIBA-GEIGY AG), and the orange-red solution obtained isdegassed in vacuo.

Using an Erichsen triangular film-drawing device, films approximately100 μm thick are drawn out onto glass and are then exposed, using aHoenle UV lamp from a distance of 20 cm at the 60% setting.

    ______________________________________                                        Exposure time                                                                   (min.) Assessment                                                           ______________________________________                                        1           The film is still liquid                                            2 orange-yellow film, still soft                                              3 orange-yellow solid film,                                                    partially soluble in DMF*                                                    5 ditto                                                                       10   orange-yellow solid film, slightly                                        soluble in DMF*                                                              15  orange-yellow solid film insoluble                                         in DMF*!                                                                     30  ditto                                                                   ______________________________________                                         *DMF = dimethylformamide                                                 

On the basis of the decrease in solubility, the above table clearlyshows that the DPP bisacrylate in this formulation has polymerizedcompletely after 15 minutes.

What is claimed is:
 1. A process for preparing or modifying polymers bya polymerization reaction or polymer-analogous reaction, which comprisespolymerizing a diketopyrrolopyrrole of the formula (I), optionally inthe presence of an appropriate comonomer or of a polymer which carriespolymerizable groups; ##STR49## in which A and B independently of oneanother are a group of the formula ##STR50## in which R₃ and R₄independently of one another are hydrogen, halogen, C₁ -C₁₈ alkyl,C₁-C₁₈ alkoxy, C₁ -C₁₈ alkylmercapto, C₁ -C₁₈ alkylamino, C₁ -C₁₈alkoxycarbonyl, C₁ -C₁₈ alkylaminocarbonyl, --CN, --NO₂,trifluoromethyl, C₅ -C₆ cycloalkyl, --C═N--(C₁ -C₁₈ alkyl), ##STR51##imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl,benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinylor pyrrolidinyl, G is --CH₂ --, --CH(CH₃)--, --C(CH₃)₂ --, --CH═N--,--N═N--, --O--, --S--, --SO--, --SO₂ --, --CONH-- or --NR₉ --, R₅ and R₆independently of one another are hydrogen, halogen, C₁ -C₆ alkyl, C₁-C₁₈ alkoxy or --CN, R₇ and R₈ independently of one another arehydrogen, halogen or C₁ -C₆ alkyl and R₉ is hydrogen or C₁ -C₆ alkyl, R₁is a radical of the formula

    --(CH.sub.2).sub.m --CH═CH--(CH.sub.2).sub.n --CH.sub.3(II)

or

    --(Y).sub.p --X--(Z).sub.r --Q                             (III)

in which m and n independently of one another are an integer betweenzero and 12, with the proviso that the sum m+n is at least 4, and p andr independently of one another are zero or 1, X is uninterrupted C₄ -C₁₈alkylene or is C₄ -C₁₈ alkylene which is interrupted one or more timesby --O--and/or --S--, --NH--, phenylene, --COO--, --CONH-- or ##STR52##in which R₁₀ is hydrogen or methyl, Y is ##STR53## --Si(Cl)₂ --,--Si(OC₂ H₅)₂ --, --Si(OCOCH₃)₂ --, --CH₂ --CH(OH)-- or --CH(CN)-- and Zis --O--, --NH--, --COO--, phenylene, ##STR54## --Si(Cl)₂ --, --Si(OC₂H₅)₂ -- or --Si(OCOCH₃)₂ --, Q is --OH, --NH₂, glycidyl, ##STR55##--CHO, --NCO, --CH═CH₂, --C(CH₃)═CH₂, --CO--CH═CH₂, --CO--C(CH₃)═CH₂, C₅-C₇ cycloalkenyl, ##STR56## --CONHR₁₁, --COOR₁₁ or --COR₁₁, in which R₁₁is hydrogen or C₁ -C₆ alkyl,or Q is ##STR57## in which s is an integerfrom 1 to 6, and R₂ is C₁ -C₆ alkyl, ##STR58## or R₁.
 2. A method forpreparing or modifying polymers by a polymerization reaction or apolymer-analogous reaction with a diketopyrrolopyrrole of formula (I):##STR59## in which A and B independently of one another are a group ofthe formula ##STR60## in which R₃ and R₄ independently of one anotherare hydrogen, halogen, C₁ -C₁₈ alkyl,C₁ -C₁₈ alkoxy, C₁ -C₁₈alkylmercapto, C₁ -C₁₈ alkylamino, C₁ -C₁₈ alkoxycarbonyl, C₁ -C₁₈alkylaminocarbonyl, --CN, --NO₂, trifluoromethyl, C₅ -C₆ cycloalkyl,--C═N--(C₁ -C₁₈ alkyl), ##STR61## imidazolyl, pyrrazolyl, triazolyl,piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl,benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl, G is --CH₂ --,--CH(CH₃)--, --C(CH₃)₂ --, --CH═N--, --N═N--, --O--, --S--, --SO--,--SO₂ --, --CONH-- or --NR₉ --, R₅ and R₆ independently of one anotherare hydrogen, halogen, C₁ -C₆ alkyl, C₁ -C₁₈ alkoxy or --CN, R₇ and R₈independently of one another are hydrogen, halogen or C₁ -C₆ alkyl andR₉ is hydrogen or C₁ -C₆ alkyl, R₁ is a radical of the formula

    --(CH.sub.2).sub.m --CH═CH--(CH.sub.2).sub.n --CH.sub.3(II)

or

    --(Y).sub.p --X--(Z).sub.r --Q                             (III)

in which m and n independently of one another are an integer betweenzero and 12, with the proviso that the sum m+n is at least 4, and p andr independently of one another are zero or 1, X is uninterrupted C₄ -C₁₈alkylene or is C₄ -C₁₈ alkylene which is interrupted one or more timesby --O-- and/or --S--, --NH--, phenylene, --COO--, --CONH-- or ##STR62##in which R₁₀ is hydrogen or methyl, Y is ##STR63## --Si(Cl)₂ --,--Si(OC₂ H₅)₂ --, --Si(OCOCH₃)₂ --, --CH₂ --CH(OH)-- or --CH(CN)-- and Zis --O--, --NH--, --COO--, phenylene, ##STR64## --Si(Cl)₂ --, --Si(OC₂H₅)₂ -- or --Si(OCOCH₃)₂ --, Q is --OH, --NH₂, glycidyl, ##STR65##--CHO, --NCO, --CH═CH₂, --C(CH₃)═CH₂, --CO--CH═CH₂, --CO--C(CH₃)═CH₂, C₅-C₇ cycloalkenyl, ##STR66## --CONHR₁₁, --COOR₁₁ or --COR₁₁, in which R₁₁is hydrogen or C₁ -C₆ alkyl, or Q is ##STR67## in which s is an integerfrom 1 to 6, and R₂ is C₁ -C₆ alkyl, ##STR68## or R₁.
 3. A polymermodified or prepared using a diketopyrrolopyrrole of formula (I):##STR69## in which A and B independently of one another are a group ofthe formula ##STR70## in which R₃ and R₄ independently of one anotherare hydrogen, halogen, C₁ -C₁₈ alkyl,C₁ -C₁₈ alkoxy, C₁ -C₁₈alkylmercapto, C₁ -C₁₈ alkylamino, C₁ -C₁₈ alkoxycarbonyl, C₁ -C₁₈alkylaminocarbonyl, --CN, --NO₂, trifluoromethyl, C₅ -C₆ cycloalkyl,--C═N--(C₁ -C₁₈ alkyl), ##STR71## imidazolyl, pyrrazolyl, triazolyl,piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl,benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl, G is --CH₂ --,--CH(CH₃)--, --C(CH₃)₂ --, --CH═N--, --N═N--, --O--, --S--, --SO--,--SO₂ --, --CONH-- or --NR₉ --, R₅ and R₆ independently of one anotherare hydrogen, halogen, C₁ -C₆ alkyl, C₁ -C₁₈ alkoxy or --CN, R₇ and R₈independently of one another are hydrogen, halogen or C₁ -C₆ alkyl andR₉ is hydrogen or C₁ -C₆ alkyl, R₁ is a radical of the formula

    --(CH.sub.2).sub.m --CH═CH--(CH.sub.2).sub.n --CH.sub.3(II)

or

    --(Y).sub.p --X--(Z).sub.r --Q                             (III)

in which m and n independently of one another are an integer betweenzero and 12, with the proviso that the sum m+n is at least 4, and p andr independently of one another are zero or 1, X is uninterrupted C₄ -C₁₈alkylene or is C₄ -C₁₈ alkylene which is interrupted one or more timesby --O-- and/or --S--, --NH--, phenylene, --COO--, --CONH-- or ##STR72##in which R₁₀ is hydrogen or methyl, Y is ##STR73## --Si(Cl)₂ --,--Si(OC₂ H₅)₂ --, --Si(OCOCH₃)₂ --, --CH₂ --CH(OH)-- or --CH(CN)-- and Zis --O--, --NH--, --COO--, phenylene, ##STR74## --Si(Cl)₂ --, --Si(OC₂H₅)₂ -- or --Si(OCOCH₃)₂ --, Q is --OH, --NH₂, glycidyl, ##STR75##--CHO, --NCO, --CH═CH₂, --C(CH₃)═CH₂, --CO--CH═CH₂, --CO--C(CH₃)═CH₂, C₅-C₇ cycloalkenyl, ##STR76## --CONHR₁₁, --COOR₁₁ or --COR₁₁, in which R₁₁is hydrogen or C₁ -C₆ alkyl, or Q is ##STR77## in which s is an integerfrom 1 to 6, and R₂ is C₁ -C₆ alkyl, ##STR78## or R₁.
 4. A processaccording to claim 1, wherein, in the formula I, A and B independentlyof one another are a group of the formula ##STR79## in which R₃ and R₄independently of one another are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₆alkoxy, C₁ -C₆ alkylamino or CN,G is --O--, --NR₉ --, --N═N-- or --SO₂--, R₅ and R₆ are hydrogen, and R₉ is hydrogen, methyl or ethyl.
 5. Aprocess according to claim 4, wherein, in the formula I, A and B areidentical and are a group of the formula ##STR80## in which R₃ and R₄independently of one another are hydrogen, methyl, tert-butyl, chlorine,bromine or CN.
 6. A process according to claim 1, wherein, in theformula I,R₁ is a radical of the formula

    --X--(O).sub.r --Q                                         (IV)

in which X is uninterrupted C₄ -C₁₂ alkylene or is C₄ -C₁₂ alkylenewhich is interrupted 1, 2 or 3 times by O and/or once by --S--, --NH--or ##STR81## r is 0 or 1 and R₁₀ is H or methyl, and Q is --OH;--CH═CH₂, --C(CH₃)═CH₂, --CO--CH═CH₂ or --CO--C(CH₃)═CH₂.
 7. A processaccording to claim 6, wherein X is --(CH₂)_(q) --, where q can be aninteger between 6 and 12,--(CH₂ CH₂ O)₂ --CH₂ CH₂ -- or ##STR82##
 8. Amethod according to claim 1, wherein, in the formula I, A and Bindependently of one another are a group of the formula in which R₃ andR₄ independently of one another are hydrogen, halogen, C₁ -C₄ alkyl, C₁-C₆ alkoxy, C₁ -C₆ alkylamino or CN,G is --O--, --NR₉ --, --N═N-- or--SO₂ --, R₅ and R₆ are hydrogen, and R₉ is hydrogen, methyl or ethyl.9. A method according to claim 8, wherein, in the formula I, A and B areidentical and are a group of the formula ##STR83## in which R₃ and R₄independently of one another are hydrogen, methyl, tert-butyl, chlorine,bromine or CN.
 10. A method according to claim 1 wherein, in the formulaI,R₁ is a radical of the formula

    --X--(O).sub.r --Q                                         (IV)

in which X is uninterrupted C₄ -C₁₂ alkylene or is C₄ -C₁₂ alkylenewhich is interrupted 1, 2 or 3 times by O and/or once by --S--, --NH--or ##STR84## r and R₁₀ are as defined in claim 8, and Q is --OH;--CH═CH₂, --C(CH₃)═CH₂, --CO--CH═CH₂ or --CO--C(CH₃)═CH₂.
 11. A methodaccording to claim 10, wherein X is --(CH₂)_(q) --, where q can be aninteger between 6 and 12,--(CH₂ CH₂ O)₂ --CH₂ CH₂ -- or ##STR85##
 12. Apolymer according to claim 3, wherein, in the formula I, A and Bindependently of one another are a group of the formula in which R₃ andR₄ independently of one another are hydrogen, halogen, C₁ -C₄ alkyl, C₁-C₆ alkoxy, C₁ -C₆ alkylamino or CN,G is --O--, --NR₉ --, --N═N-- or--SO₂ --, R₅ and R₆ are hydrogen, and R₉ is hydrogen; methyl or ethyl.13. A polymer according to claim 12, wherein, in the formula I, A and Bare identical and are a group of the formula ##STR86## in which R₃ andR₄ independently of one another are hydrogen, methyl, tert-butyl,chlorine, bromine or CN.
 14. A polymer according to claim 3, wherein, inthe formula I,R₁ is a radical of the formula

    --X--(O).sub.r --Q                                         (IV)

in which X is uninterrupted C₄ -C₁₂ alkylene or is C₄ -C₁₂ alkylenewhich is interrupted 1, 2 or 3 times by O and/or once by --S--, --NH--or ##STR87## r and R₁₀ are as defined in claim 3, and Q is --OH;--CH═CH₂, --C(CH₃)═CH₂, --CO--CH═CH₂ or --CO--C(CH₃)═CH₂.
 15. A polymeraccording to claim 14, wherein X is --(CH₂)_(q) --, where q can be aninteger between 6 and 12,--(CH₂ CH₂ O)₂ --CH₂ CH₂ -- or ##STR88##